Iminophosphorane complexes

Related studies were recently reported by Contel, Urriolabeitia et al. using organogold(III) iminophosphorane complexes as catalysts for the addition of... 

A series of cationic, strapped, r)6 ri1 ri1-arene complexes of ruthenium(II) (82) containing both carbon and phosphorus as the auxiliary atoms has been obtained by a coupling reaction of the iminophosphorane complexes 83 with an excess of 1, l-diphenyl-2-propyn-l-ol, the p-cymene in 83 being displaced by one of the phenyl... 

Remarkably the use of benzyne-zirconocene allows the formation of unexpected new complexes as the first q1 -iminozirconocene 48, the unprecedented phosphazide and iminophosphoranes complexes 34-46, or the unique so far stable pentacoordinated organo zirconocene-ate complexes 20,21,22-G4,22-G8, 24-G3-G2,25-31. 

The reaction of keto-stabilised ylides with ra/7J-[PtCl2(NCR)2] (R = C6F5, Me) does not lead to the expected bis-ylide complexes, but to N-bonded P-iminopho-sphorus ylide complexes, 63 and 64, or iminophosphorane complexes 65, depending upon the nature of the ylide, R and the reaction conditions. 

Sarsfield MJ, Steele H, Teat SJ (2003) Uranyl bis-iminophosphorane complexes with in- and out-of-plane equatorial coordination. Dalton Trans 3443-3449. doi 10.1039/B304602H... 

The reaction of the lithium compound 55, accessible from the iminophosphorane CH2(SiMe3)PPh2=NSiMe3 and BuLi, with PbCl2 gives colorless crystals of the lead complex 56 in 50% yield (Equation (21)).77 Similarly, treatment of PbCl2 with the lithium compound 57 affords yellow crystals of the donor-stabilized lead(ll) diaryl 58 in 70% yield (Equation (22)).78... 

Recently, the potential of organometallic iminophosphoranes as synthetic components for radiopharmaceutical agents has been reported. In nuclear medicine Rh is currently being used as a radioisotope for diagnostics and cancer therapy. A complex of Rh with organometallic iminophosphoranes, such as 43 (Scheme 22), could represent a novel type of radiopharmaceutical [93ZN(B)1381]. 

Although this review is by no means exhaustive, it should present an impression of the importance of iminophosphoranes as versatile synthons in heterocyclic synthesis. Much attention was paid to the aza-Wittig reaction, which enables the preparation of a wide range of simple and complex heterocyclic systems. 

Iminophosphoranes, mercuration, 2, 432 (Iminophosphoranyl)ferrocenes, synthesis, 6, 202 Imino-pyrrolate systems, with zirconium, 4, 1138-1139 Imino-pyrrolides, with Zr(IV) and Hf(IV), 4, 780 Imino-pyrrolyl ligands, in chromium complexes, 5, 355 Iminosilanes, reactions, 3, 440 Imprinted complexes, on oxide surface, 12, 810 Impurities, glovebox techniques, 1, 215 Inclusion chemistry... 

Co11 complexes containing phosphoramides (O = P(NR2)3)591 iminophosphoranes (RN = PPh3)592 and phosphinates ( 02PR R2)593 are known, as are distorted octahedral complexes containing the neutral chelating ligands (171),m (172)595 and (173).596... 

The metathesis of symmetrical aliphatic carbodiimides is also catalyzed by tungsten imido complexes above 140 Other carbodiimide metathesis catalysts include Cr(ll)/Si02/ iminophosphoranes, imido circonocenes, guanidine supported titanium complexes and group 14 amide complexes. ... 

For several years, Streubel and coworkers have been exploring the chemistry of nitrilium phosphine ylides that contain low-valent organophosphorus fragments, such as complex (19) (Scheme 3). In their latest contributions to this area, they have investigated the reactions of complex (19) with phosphoranes and iminophosphoranes which have led to a number of new species containing ylidic moieties, such as the tricyclic complex (20), and 2H-l,2-azaphosphole complexes (21) and (22). Similarly, treatment of other low-valent organophosphorus complexes such as phosphinidine species (23) with stabilised phosphoranes produces new ylidic-aducts (24) and (25) (Scheme 4). ... 

Ylides Coordinated to Metals. - Complexes of iminophosphoranes have attracted attention due to their potential application as catalysts for the polymerisation of olefins. A recent contribution to this field reports the coordination of sterically hindered iminophosphorane (73) towards titanium and zirconium tetrachlorides. Treatment of TiCb with (73) led to the phosphoranato complex (74) whereas ZrCU was unreactive. However, treatment of Zr(NMe2)4 with (73) led to complexes (75) and (76) (Scheme 23). The structures of ligand (73) and... 

Argues, A., Molina, P. Bis(iminophosphoranes) as useful building blocks for the preparation of complex polyaza ring systems. Curr. Org. Chem. 2004, 8, 827-843. 

Several new complexes of iminophosphoranes have been reported by Cavell and co-workers (Scheme 9). Reaction of dimethyl zinc with bis- trimethylsilyl-imino-diphenylphosphorano methane (61) yields zinc complex (62) via elimination of methane. Complex (62) did not react with adamantyl nitrile or isonitrile but does undergo nucleophilic addition reactions with hetereroallenes such as carbodiimides and isocyanates. Thus, treatment of (62) with adamantyl isocyanate produces the novel tripodal alkyl zinc complex (63). Iminophos-phorane (61) reacts with [Sm(NCy2)3(THF)] and tetrakis(benzyl)zirconium(IV)... 

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